Production of cyclobutano compounds



United States Patent Gfitice 2,714,617 Patented Aug. 2, 1955 PRODUCTIONF CYCLOEUTANO COMPOUNDS Rex E. Lidov, Denver, (1030., and HenryBluestone, Shaker Heights, Ohio, assignors, by mesne assignments, toShell Development Company, Emeryville, Caiiit'., a corporation ofDelaware No Drawing. Application January 7, 1953, Serial No. 330,165

6 Claims. (Cl. 260--648) The present invention is a continuation-in-partof copending application Serial No. 156,716, filed April 18, 1950, nowU. S. Patent No. 2,676,132.

The present invention relates to novel, polycyclic compositions ofmatter which are unique both as to structure and method of formation.They are cyclobutano compounds containing, in all, seven cycles, and areformed by a single reaction from the tetracyclic compounds, such as1,2,3,4,l0,l0-hexachloro-1,4,4a,5,8,8a-hexahydrol,4,5,S-dimethanonaphthalenedescribed and claimed in the copending application of Rex E. Lidov,Serial No. 325,881, filed December 13, 1952.

The compounds of the present invention are prepared by a novelinteraction of the two olefinic linkages in the above mentionednaphthalene. This reaction can be exemplified as follows.

The interaction of the two olefinic linkages results in the formation ofa cyclobutane structure which can be more readily visualized in thethree dimensional presentation below:

The following examples illustrate the process of the present invention:

Example I l,2,3,4,10,10 hexachloro l,4,4a,5,8,8a hexahydro-1,4,5,8-dimethanonaphthalene (M. P. 2-40-242 C.; 0.1 mole) (identifiedin Lidov, Serial No. 325,881, as betahexachlorotetracyclododecadiene)was dissolved in 300 m1. of diethyl ether which had been dried for 18hours over calcium chloride. The solution was held at 20 C. andanhydrous hydrogen bromide was passed into it for a 12-hour period.Concentration of the diethyl ether solution caused the precipitation ofa high melting crystalline solid. Repeated recrystallization of thissolid from mixtures of acetone and hexane yielded a crystalline productmelting, with decomposition, at 288289 C.

Analysis.-Calculated for CizHaCls: Carbon, 39.49%, hydrogen, 2.2%,chlorine, 58,30%. Found: Carbon, 39.75%, hydrogen, 2.32%, chlorine,58.3%.

This compound does not undergo reactions of olefins. For example it hasa hydrogenation value of zero, does not yield an epoxy derivative, failsto react with stronger oxidizing agents such as KMnOt and CrO3, fails toadd halogens, and does not react with phenyl azide. This compound is thecyclobutano compound previously represented structurally.

Further concentration by evaporation of the diethyl ether mother liquorfrom which the above product had been separated resulted in theprecipitation of a second crop of crystals which, crude, melted over therange of -145 C. Recrystallization of this material from a mixture ofacetone and hexane produced a white crystalline solid melting at 1l0111C.

AnaZysis.-Calculated for CizHsClsBrz Carbon 32.32%, hydrogen, 2.03%,halogen calculated as chlorine, 55.67%, Found: Carbon, 32.5%, hydrogen,2.06%, halogen calculated as chlorine, 55.5%.

This material is therefore 6-bromo-l,2,3,4,10,10-hexachloro1,4,4a,5,6,7,8,8a octahydro l,4,5,8-dimethanonaphthalene represented bythe following: formula:

01 H H 01 g.

This compound is described and claimed in said Lidov application.

Example I] 1,2,3,4,10,10 hexachloro l,4,4a,5,8,8a hexahydro1,4,5,8-dimethanonaphthalene (M. P. 240242 C.; 0.1 mole) was dissolvedin 650 ml. of glacial acetic acid; the solution was heated to about 50C. and anhydrous hydrogen bromide was passed into it for a period ofabout three hours. The solution thus obtained was distilled underreduced pressure to remove most of the acetic acid and the HBr dissolvedtherein. A White crystalline precipitate was obtained from the residualsoltuion. This white crystalline solid was recrystallized fromacet0nehexane as before and the crystalline product, melting, withdecomposition at 288-289 C. was obtained. This material was identicalwith the cyclobutano product obtained in Example I.

The reaction of l,2,3,4,7,7-hexachlorobicyclo-(2.2.l)- 2,5-heptadienewith l-methyl, 2-methyl and 5-methyl- 1,3-cyclopentadienewill result inS-methyl, 6-metl1yl and 9-methyl derivatives or"123,4,l0,l0-hexachloro-l,4,4-a,

5,8,8a-hexahydro-l,4,5,8 dimethanonaphthalene having structures as shownbelow.

5methy1 compound G-methyl compound (Compound B) (Compound A) 9-methy1compound (Compound C) These compounds will each likewise undergo theintern action of the two olefinic bonds in the 2,3 and 6,7 posi tionsrespectively when treated with hydrogen bromide in the mannerhereinbefore shown to result in the structures represented threedimensionally below:

Derived from Compound C The unique compounds of the present inventionare valuable as insecticides. For example, the compound of Example IIhas exhibited insecticidal potency four times that of DDT.

In addition to their insecticidal activity, the present compounds areuseful as impregnants and fire retardants.

In their insecticidal use, the present compounds can be formulated asthe sole toxic ingredient or in combination with other insecticides,synergists or knockdown agents. Formulations can be aqueous dispersions,oil

solutions, dusts, wettable powders, aerosols, or any other types knownin the art.

In the structural diagrams in the foregoing specification and followingclaims, the dotted lines and solid lines are merely for the purpose ofrepresenting three-dimensional configurations and not any difference inthe type of bonding between the atoms.

We claim as our invention:

1. As a new composition of matter a compound having the structure:

wherein A, B, and C are of the group consisting of hydrogen and methyl,said compound containing not more than one methyl group.

2. As a new composition of matter a compound having the structure:

3. As a new composition of matter a compound having the structure:

4. As a new composition of matter a compound having the structure:

5. As a new composition of matter a compound having the structure:

6. The method which comprises heating a compound of the group consistingof (a) 1,2,3,4,10,10-hexachloro- 1,4,4a,5,8,8a hexahydro 1,4,5,8dimethanonaphthalene melting at about 240-242" C., (b) its S-methylderivative, (0) its 6-methyl derivative, (d) its 9-methyl 5 derivativewith hydrogen bromide in the presence of a solvent and recovering asaturated heptacyclic compound.

References Cited in the file of this patent UNITED STATES PATENTS LidovApr. 21, 1953 Lidov Apr. 21, 1953 OTHER REFERENCES

1. AS A NEW COMPOSITION OF MATTER A COMPOUND HAVING THE STRUCTURE: